Bis(triorganotin) salts of dibasic acids and the preparation thereof



United States Patent 3 409 652 BIS(TRIORGANOTIN) SAl.TS OF DIBASIC ACIDSAND THE PREPARATION THEREOF James A. Horrocks, Ipswich, England,assignor to Bakelite Xylonite Limited, a corporation of Great Britain NoDrawing. Filed Sept. 7, 1965, Ser. No. 485,580 Claims priority,application Great Britain, Sept. 11, 1964, 37,297/64 9 Claims. (Cl.260429.7)

This invention relates to a stabilizer composition for polymericsubstances having the formula The present invention relates toorgano-tin compounds, methods for their manufacture, and polymericcompositions containing them.

Many organo-tin compounds have been prepared which have found use asstabilizers for polymeric compositions, for example for polyvinylchloride. More recently, thiotin compounds have been mcreasinglyemployed for this after prolonged processing.

It is an object of the present invention to provide a new compoistionhaving improved resistance to discoloration during processing.

It is a further object of the invention to provide an improvedstabilizer for polymeric compositions, especially polyvinyl chloride.

one or more compounds of the formula XH wherein X represents a saturatedor unsaturated dibasic divalent radical free from sulphur.

3,409,652 Patented Nov. 5, 1968 5%, preferably about 2%, by weight ofthe uct, based on the weight of the polymer.

reaction prodhe reaction product normally comprises a compound of theFormula I containing stabilizers, is achieved more cheaply.

When Y and Y are different and/or R R R and The following examplesillustrate the invention. In Examples I to 6, the compound named at thehead of the contribute largely to the stabilizing elfect, although it isto is in no Way limited by and their effects. Example 1 (Stabilizer RV59) Composition comprising OOC.OH=CH.COOO;H1 Bis (dibutyl tin2-ethy1-hexyl maleate) malea'te 26 gm. 2-ethylhexanol and 19.6 gm.maleic anhydride are heated at 110 C. until a clear liquid is obtained.Then ml. of benzene and 24.8 gin. dibutyl 3 v the product as a clearliquid. Refractive index 1.4822 at 25 C.

stabilizing effect of the product is All three stabilizers gaveapproximately the same stability, e.g. Clear after 35 mins. but slightlyyellow at 40 mins.

Breon 202 is a vinyl chloride/vinylidene chloride cpolymer containing 4%vinylidene chloride and is manufactured by British Geon Ltd.

Example 2 (Stabilizer RV 61) Composition containing 04119 O O 0.CH=CH.CO 0 0511 Sn 04Hq Sn C4119 SCHzCOOCsIIu S'dibutyl tin mono (2 ethylhexylthioglycollate) mono maleate salt of dibutyl tin mono(2-ethy1hexylmaleate) This stabilizer was prepared by reacting 0.20 moledibutyl tin oxide, 0.10 mole maleic anhydride, 0.098 mole 2 ethylhexylthioglycollate, 0.098 mole 2 ethylhexyl maleate. These were mixedtogether with stirring and heated at 120 C. until all water had beenevolved. The product was a clear yellow slightly viscous liquid. Ref.Index 1.5110 at 25 C. (measured on an Abbe refractometer).

This was then tested as a stabilizer by incorporating into polyvinylchloride and milling on a two roll mill at 175 C. removing samples every5 minutes to compare color.

Vybak DVY 18 100 100 Stabilizer RV 61 Dibutyl tin maleate "i." 2

Wax

Stabilizer RV 61 gave a glass clear color after 60 mins. whilst dibutyltin maleate gave a yellow color after 35 mins. No plate out occurred.

Vybak DVY 18 is polyvinyl chloride manufactured by Bakelite Limited.

Example 3 (stabilizer RV 60) Composition comprising Sn 04119 $01120 O 0031-1 7 S-dibutyl tin mono (2 ethylhexyl thioglyeollate) mono maleicacid salt of S-dibutyl tin mono (2 ethylhexyl thioglyeollate) This wasprepared using the procedure of Example 2, by reacting 0.02 mole dibutyltin oxide, 0.100 mole maleic anhydride, and 0.196 mole 2-ethylhexylthioglycollate. The product Was a clear yellow slightly viscous liquid.Ref. Index 1.5110.

This was then tested in Vybak DVY 18 against dibutyl tin maleate. Thecompound stabilized with dibutyl tin maleate turned yellow after 35mins. whilst that stabilized 'With RV 60 was clear after 60 mins.

Again no plate out occurred.

Example 4 (Stabilizer RV 61A) Composition containing S-dibutyl tin mono(Z-ethylhexyl thioglycollate) mono maleic acid salt of dibutyl tin2-ethylhexyl maleate. i

This product was preparedby reacting 248.9 gm. dibutyl tin oxide, 102.1gm. 2-ethylhexyl thioglycollate, 49 gm. maleic anhydride and 114 gm.Z-ethylhexyl maleate. These were mixed together with stirring and heatedat C. until all water had been evolved. The product was a yellow liquid.Refractive Index at 25 C.=1.5062.

Example 5 (Stabilizer RV 62) Composition comprising dibutyl tin mono(2-ethylhexyl maleate) mono maleic acid salt of dibutyl tin phenylmercapto acetate.

This product was prepared by reacting 248.9 gm. dibutyl tin oxide, 84.1gm. phenylmercaptoacetic acid, 49 gm. maleic anhydroxide and 114 gm.2-ethylhexyl maleate. These were mixed together with stirring and heatedat 120 C. until all water had been evolved. The product was pale yellowliquid. Refractive Index at 25 C.=1.5235.

Example 6 (Stabilizer RV 63) Composition comprising dibutyl tin mono(2-ethylhexyl maleate) mono malonic acid salt of dibutyl tinphenylmercaptoacetic acid.

This compound was prepared by reacting together 248.9 gm. dibutyl tinoxide, 52.02 gm. malonic acid, 114 gm. Z-ethylhexyl maleate, and 84.1gm. phenylmercaptoacetic acid. These were mixed together with stirringand heated at 120 C. until all water had been evolved. The product was apale yellow liquid. Refractive Index at 25 C.=1.5211.

Example 7 All the above stabilizers of corporated into a polyvinylmilling and using the following Examples 4 to 6 were inchloridecomposition by formulation:

Parts by. weight Breon 202 resin 100 Stabilizer 2 Wax 1.5

Each composition was milled on a two roll mill at C. removing samplesevery 5 minutes to observe color development.

The compositions were compared with dibutyl tin maleate as a standardstabilizer.

RESULTS Stabilizer: Time taken for initial c'olor', mins. Dibutyl tinmaleate 35 RV 61A 40 RV 62 60 RV 63 60 No plate out occurred with any ofthe stabilizers of this invention.

What is claimed is:

1. A stabilizer composition for polymeric substances, which comprisesone or more water-free compounds of the formula wherein R R R and R areselected from the group consisting of alkyl, alkaryl, aralkyl or arylradical having from 2 to 20 carbon atoms, Y and Y each represent amonobasic radical other than the radical of a fatty acid, and Xrepresents a saturated or unsaturated dibasic divalent radical free fromsulphur.

2. The composition of claim 1 wherein R R R and R are n-butyl radicals.

3. The stabilizer composition of claim 1 wherein X is a dibasic radicalof compounds having 2 to 20 carbon atoms and having terminal groupsselected from the group consisting carboxyl and hydroxyl.

4. The stabilizer composition of claim 1 wherein X is a dibasic radicalof compounds selected from the group or itaconic acid. composition ofclaim 1 wherein Y; or Y are monobasic radicals of compounds having 2 to20 carbon atoms and having terminal groups selected from the groupconsisting of carboxyl, hydroxyl and mercaptan.

6. The stabilizer composition of claim 1 wherein Y or Y; are monobasicradicals of compounds selected from the group consisting of 2-ethylhexylmaleate, Z-ethylhexyl thioglycollate, fi mercaptoproprionic acid,phenylmercaptopropionic acid or of lauryl mercaptan.

7. A process for the manufacture of a stabilizer composition having theformula wherein R R R and R are selected from the groups consisting ofalkyl, alkaryl, aralkyl and aryl radical having from 2 to 20 carbonatoms, Y and Y, are monobasic monovalent radicals other than radicals ofa fatty acid and X is a dibasic, divalent radical free from sulfur whichcomprises reacting together at least one compound of the formula R2 atleast one compound of the formula Sn=0 R.

at least one compound of the formula YH and at least one compoun whereinsaid temperature References Cited UNITED STATES PATENTS 2,857,41310/1958 Weinberg TOBIAS E. LEVOW, Primary Examiner. W. F. W. BELLAMY,Assistant Examiner.

